JPS5829818A - Silicon-end polyurethane polymer - Google Patents

Abstract

The method comprises reacting a polyurethane prepolymer having terminal active hydrogen atoms with an isocyanato organosilane having a terminal isocyanate group and at least one hydrolyzable alkoxy group bonded to silicon. The moisture-curable polymer obtained by this method can advantageously be used in sealant compositions. The polymer presents a very rapid cure rate in the presence of moisture, and it is stable under unhydrous conditions.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to moisture-curable silicon-terminated organic polymers, processes for their preparation, and moisture-curable sealant compositions comprising moisture-curable polymers of this type.

U.S. Pat. No. 3,632,557 teaches a silicon powdered 14M homopolymer that can be cured at room temperature in the presence of moisture. The patent teaches that this oak polymer can be used for coatings, corings and seven-rings after incorporation of fillers normally incorporated into elastic compositions.

In fact, U.S. Pat. No. 3,979,344 and U.S. Pat. No. 4,222,925
! No. F 3,632,557 teaches a sealant composition that can be cured at room temperature in the presence of moisture, consisting of an organosilicon polymer and certain additive materials. Thus, the '344 patent discloses the use of N-(β-aminoethyl)-r-aminopropyltrimethoxysilane in sealant compositions containing silicon-terminated organic polymers of this type. No. 4,222,925 teaches the addition of certain carbon black fillers to such compositions. These patents cover non-porous surfaces,
In particular, the utility of silicon-terminated organic polymers for forming strong bonds to glass, and previously the utility of sheeting compositions containing said polymers, is taught.

The silicon-terminated organic composites of the present invention are likewise moisture curable at room temperature and can be similarly formulated into sheet compositions comprising fillers and other additives. Like conventional materials, the inventive polymers and compositions provide non-porous surfaces,
For example, they exhibit particularly good adhesion to glass and facilitate the use of polymers and sealant compositions formulated therewith in industrial applications, for example as sealants for automotive glass such as windshields. It is particularly characterized by a very rapid curing speed.

The silicon-terminated organic polymer of U.S. Pat. No. 3,632,557 is a polyurethane prepolymer having terminal incyanate groups that contains an alkoxysilane and isocyanate-reactive mercapto groups or primary or secondary It is produced by reacting with a silicon compound having an amino group. Upon reaction of the terminal incyanate groups of the polyurethane prepolymer with the mercapto or amino groups, a moisture-curable polymer having terminal hydrolyzable alkoxysilane groups is produced.

These terminal alkoxysilane groups react in the presence of atmospheric moisture to form siloxane (-8l-0-8l-) groups, possibly via intermediate silanol formation. The formation of chloroxane bonds not only crosslinks and cures the moisture-curable polymer, but also promotes adhesion of the monomer to non-porous surfaces, such as glass surfaces. Hydrolyzable alkoxine 2 groups form particularly strong bonds in the presence of atmospheric moisture.

According to the invention, a polyurethane prepolymer is similarly reacted with an organosilane compound having one or more hydrolyzable alkoxycine groups.

However, according to the present invention, the polyurethane prepolymers have terminal active hydrogen atoms present in groups such as hydroxyl groups, mercapto groups or primary or secondary adenogroups. These active hydrogen atoms are reacted with incyanate groups present in the organosilane compound. As in conventional methods, urethane, thiourethane, or urea groups are produced by reaction, but the properties of these linking groups to attach terminal silane groups to polyurethane prepolymers are different from those known in conventional methods. The different sealants and improved properties of the polymers and sealants of the present invention are illustrated. For purposes of illustration, U.S. Pat. No. 3,632,557 uses the formula %
Formula % [In the formula, R is lower alkyl, hb, n' is a divalent bridging group, and 2 is st9 is NR'' (V is H or lower alkyl)] and the formula The reaction of OCN (-polyurethane polymer + NGO with isocyanato-terminated polyurethane polymer is shown. The reaction of the two compounds is as follows: In contrast, according to the invention, an isocyanato-terminated organosilane compound, such as (RO)s -R'-NGO, is used to form a polyurethane prepolymer having active hydrogen atoms. For example, by reacting with Hz(-polyurethane polymer + ZH (wherein 2 is o, s, t or NR//TE, and Secitebi is lower alkyl as much as It), the terminal end of the polymer of the following structure is obtained. give rise to a foundation.

U.S. Pat. No. 3,632,557 teaches in detail the preparation of incyanato-terminated polyurethane polymers by reaction of organic polyisocyanates and polyhydroxy compounds. In this reaction, a molar excess of polyisocyanate is used so that the resulting polymer has an inocyanate content. Exactly the same procedure is used except that the hydroxy compound is used in molar excess with respect to the polyisocyanate so that the resultant has a human tetraxy terminus.
compounds and reagents can be used in the present invention to produce the prepolymers of the present invention. Precisely the same polyols, such as polyester polyols, lactone polyols produced by the polymerization of alkanol lactones such as lactones, especially 8-cablocktone, compounds such as castor oil, and especially polyether polyols. It is self-contained in use as in conventional methods. Polyether polyols can be produced by forming alkylene oxide adducts of the above-mentioned polyols and polyester polyols, which can be produced by reacting the alkylene oxide with a substance such as castor oil.

However, preferred polyether polyols are polyoxyalkylene polyols, such as polyoxyalkylene diols produced by homopolymerization or copolymerization of materials such as ethylene oxide and propylene oxide. Polyoxyalkylene triols, such as linear compounds with hydroxyl groups or branched polyether chains, can be used as starting compounds in mixtures with diols.

jl! Suitable polyols are polyhydroxypolysulfide polymers of the formula % where X and Y are each divalent aliphatic radicals and have a weight of from 1 to 1000.

Polyurethane prepolymers with terminal mercapto groups are obtained by analogous reactions between thio compounds and polyisocyanates similar to the polyester and polyether compounds mentioned above.

In a similar manner, polyurethane prepolyole having wood end amino groups is mixed with polyisocyanate and primary and (Makuha)
They are produced by condensation reactions with polyamines having secondary amino groups, such as diamines and triamines.

The use of prepolymers made from polyols is preferred in the present invention. This type of polyol having two or more hydroxyl groups generally has a molecular weight of 500 to 60,000,
And it can be either a polyester polyol or a polyether polyol, the latter being preferred.

The polyols or polyol mixtures used in the invention generally have a hydroxyl weight range of: 50 to 2000. Preferred polyoxyalkyles/polyols,
For example, polyoxypropylene has a hydroxyl equivalent weight of 200 to 2000.

As mentioned above, triols that lead to the formation of branched polyurethane prepolymers can be used to replace some of the diols normally used in reactions with polyisocyanates.

A further preferred embodiment of the invention is to use water in place of some of the polyol compounds or mixtures of polyols. Water produces carbon dioxide upon reaction with isocyanate, which in turn produces amino groups. The latter further reacts with isocyanate groups to form urea groups. According to the invention,
It has been found that the resulting prepolymers containing both urethane and urea groups have improved thermal stability and weatherability. Although applicants do not wish to be bound by theory, it is believed that the synergistic presence of urea and urethane groups within the grebolimer precedes the onset of degradation of the polyurethane polymer by lightning-like weathering phenomena in response to heat and ultraviolet light. It is possible to lengthen the lag period.

In this embodiment, a number of equivalents of water equal to 25,111 equivalents of isocyanate-reactive OH groups provided by the polyol can be used. Preferably,
The polyol conveniently used in this embodiment is an aliphatic polyol, such as a polyoxyalkylene polyol.

The organic polyisocyanate used in the present invention to form the prepolymer having 1c atoms was also used in US Pat. No. 3,632,557. That is, they are aliphatic, aliphatic, araliphatic, aromatic polyisocyanates, preferably diinocyanates and (t)
It is tri-inocyanate. Particularly preferred materials for use in the present invention are 4,4-diphenylmethane diisocyanate with aromatic character, the cycloaliphatic diisocyanate 3-iso7anatomethyl-3.5°5-trimethylcyclohexyl inocyanate, known as isophorone diisocyanate, and Product name [Hyl@
n.) dicyclohexyl-4, commercially available at WJ;
4'-methane diisocyanate. Mixtures of two or more of these preferred materials are also preferred for use in the present invention.

The reaction of polyurethane with polyol, polythiol or variagin can be carried out preferably in the presence of a catalyst. For the production of urethanes, for example stannous salts of carboxylic acids, such as stannous octoate, stannous oleate, etc.
Tin, stannous acetate, and stannous roughinate are known catalysts of this type. Additionally, like tertiary amines and tin mercaptides, dialkyltin dicarboxylates, such as diptyltin dilacrate and dibutyltin diacetate, are known in the art as urethane catalysts. Still other catalytic materials are known to those in the dental arts. The amount of catalyst used, depending on the nature of the incyanate, is generally o, oosN5 - by weight of the mixture to be catalyzed.

Suitable conditions for this type of reaction are well known in the art. For example, the components are allowed to react at temperatures between 0<0>C and 120<0>C, preferably between 25<0>C and 90<0>C, until no incyanate can be detected by infrared analysis. The reaction is carried out in an inert atmosphere, such as a nitrogen blanket, and under anhydrous conditions.

The resulting prepolymers with end groups with active hydrogen atoms have a molecular weight of 3,000 to 180,000 and a total molecular weight of 180,000,00.
Preferred prepolymers having a molecular weight of 0 to 15,000 facilitate reaction with the isocyanatoorganosilane compound used to "block" the prepolymer and provide a 7-land "blocking" tail. It has a moderate viscosity which makes it easy to incorporate into the composition.

The organic compound reacting with the prepolymer has the formula % (formula %) (where %R is a divalent organic group, R' is hydrogen or, for example, alkyl having 1 to 4 carbon atoms, is, for example, a hydrolyzable alkoxy group having 1 to 4 carbon atoms,
m is an integer from 1 to 3). The group R is a terminal isocyanate group and an alkoxy 7
Various structures that produce stable buri and tsuji between orchid groups
- can have. Numerous structures for this type of isocyanatoalkoxysila/compounds are disclosed, for example in U.S. Pat.
, 146,585, columns 4 and 5. However, preferably R has at least 3 carbon atoms.
and a particularly preferred material for use in the present invention is a lower alkyl group having r-isocyanatopropyl-
triethoxysilane and r-incyanatopropyl-
It is trimethoxysilane.

When a polyurethane prepolymer having active terminal hydrogen atoms is reacted with an incyanato alkoxysilane such as those described above in approximately stoichiometric amounts, the incyanato groups of the latter material react with an equivalent amount of terminal active hydrogen atoms of the prepolymer. to produce a stable prepolymer with terminal alkoxy heptad groups. The number of alkoxy groups present in the system will determine the degree of crosslinking of the polymer when cured by exposure to moisture, such as atmospheric moisture.

The reaction between the prepolymer and the incyanato alkoxysilane is carried out under anhydrous conditions and preferably in an inert atmosphere, such as a nitrogen plaque, to prevent premature hydrolysis of the alkoxysilane groups. The reaction is suitably carried out at 0°C to 150°C, preferably at 25°C, until the isocyanate groups can no longer be detected by infrared analysis.
Perform at ~80°C.

As mentioned above, upon exposure to moisture, e.g. atmospheric moisture, the alkoxysilane group hydrolyzes, possibly forming the corresponding silanol intermediate, and ultimately leading to curing and bonding of the material to a substrate such as glass. Mokurasu siloxane (
-St -g) bond will occur.

The rate of hydrolysis of alkoxysilanes by moisture, and thus the rate of crosslinking, is enhanced by the use of catalysts known to promote the condensation of silanols. These substances are
Metal salts of carboxylic acids, such as tin salts, organosilicon titanates, alkyl titanates, and the like. Diptyltin diacetate is the preferred catalyst in the present invention, To9, and preferably 0.1 to 1% by weight of the polymer, more preferably 0.2 to 0.
．． Used in an amount of 6 wt. Catalysts of this type are therefore preferably present as a component in sealant compositions comprising the polymers of the present invention.7 Furthermore, quaternary arylalkyl or aralkyl ammonium compounds, especially quaternary ammonium It has been found that the presence of a hydroxide, such as benzyltrimethylammonium hydroxide, unexpectedly and unexpectedly accelerates the curing of the polymers of the present invention, and that this material is useful in sealant compositions comprising the polymers of the present invention. It is preferably blended within. For example, a rapid curing action is particularly necessary when a composition containing the polymer of the invention, such as a 7-lant composition, is required to adhere quickly to the parts to be assembled with a sealant. . This type of rapid curing is an important factor, for example, during the assembly and installation of windshields in the automobile industry.

When formulating sealant compositions, the polymers of the present invention are combined with fillers and cooling agents known in the art for use in elastomeric compositions. The addition of substances in this ridge can improve anatomical properties such as viscosity, flow rate,
You can change the amount (1mg) etc. To prevent premature hydrolysis of moisture-sensitive polymer groups,
The filler should be completely dry before mixing. Exemplary filler materials and additives are various materials such as carbon black, titanium dioxide, clay, calcium carbonate, surface treated silica 1 UV stabilizers, antioxidants, and the like. However, this example line is for illustration purposes only and is not intended to be limiting.

As mentioned above, monomeric alkoxy 7-lanes, preferably monomeric aminoalkoxy 2-lanes, are preferably physically incorporated with the polymer into sealant compositions of this type. Upon hydrolysis, the monomeric alkoxysilane acts as a further crosslinking agent between the polymer molecules and (also #'i) between the polymer molecules and a surface, such as a glass surface, to which the sealant composition can be applied. . In particular, N-alkyl-aminoalkyltrialkoxysilane monomers, especially compounds whose alkyl groups are all lower alkyl groups having 1 to 4 carbon atoms, are preferably used as auxiliary crosslinking agents for this woodcutter. Preferred cross-linking agents for E% are N-(β-aminoether)-r-aminoprobyltrimethoxy77 run of the formula %formula%) () (cycilylprobyl)-ethylenediamine and the formula%formula%). be. The latter is the 4.22nd peak in the United States.
These are the same compounds taught to be useful as sealant additives in US Pat. No. 2,925.

As mentioned above, the presence of quaternary ammonium compounds, particularly quaternary ammonium hydroxide, greatly increases the curing rate of the polymers of the present invention and sealant compositions containing them. These accelerators are present in the composition in an amount of 0.1 to 5% by weight of the polymer to be cured.

The use of quaternary ammonium compounds, such as hydroxides, as catalysts for the curing of organopolysiloxane resins is known in the art.

For example, a US patent! ! The specification of No. 2,759,007 is
The production of low molecular weight polysiloxanes by hydrolysis and condensation of M,t-dialkyldialkoxy heptadranes is disclosed. As disclosed in this patent, dialkylfucrosiloxanes consisting of 3-4% monomer units constitute the majority of the product. These cyclic siloxas/oligomers are difficult to condense or polymerize into high molecular weight materials. However, alkaline catalysts, such as quaternary ammonium hydroxide, have been taught to facilitate this reaction. However, the reaction is probably not appropriate for the percentage of hydrolysis of the alkoxysilane to form the polymeric organic compound via the intermediate silanol.

No. 3,208,972 describes the preparation of monomethylsiloxane t-m by hydrolyzing methyltrimethoxysilane or methyltriethoxysilane in the presence of an alkaline substance, such as quaternary ammonium hydroxide. discloses a method to do so. However, the reaction is limited to the hydrolysis of these monomers, limited to the production of sun-in-silica polymers consisting of CHISlO8/repeat units, and must be carried out in water. At least 6 moles of water per mole of initial silane are required to form the siloxane product in the patent.

The invention and many of its features will be better understood by reference to the following specific examples, which are presented for illustrative purposes. In the following examples, the nine polyether diols used are approximately 2,0
It has an average molecular weight of 0.00 and has the trade name [Pull 2 Call
luracol) 1'2010J, which is commercially available. Unless otherwise specified, the polyether triol in the example is about 4
It is a dipropylene triol in polio having an average molecular weight of ,000 and commercially available under the trade name "Pul2col TPE-4542J".

Triols are produced by polymerizing propylene oxide to a trihydric alcohol starting material, such as glycerin or trimethylolpropane. Unless otherwise specified, the incyanatoalkoxysilane used in the examples is r-isocyanatopropyltriethoxysilane.

Example 1 A sila/terminated prepolymer having a linear polyether structure is produced as follows. polyether diol 3
43.5 g (0,343 eq.), 36.0 g (0,286 eq.) 4,4'-diphenylmethane diisocyanate, and 0.0 g (0,286 eq.) of diptyltin dilaurate as catalyst.
02.9 were thoroughly mixed in the reaction vessel in the presence of a very small amount of antifoaming agent. Due to the reaction between incyanate and hydroxyl groups, the temperature of the mixture is raised to 45° C. during mixing. The temperature is then raised to 75° C. and maintained for about 3 hours until incyanate can no longer be detected by infrared spectroscopy.

Then incyanatoalkoxysilane 14.1.9 (
0.057 fit) is added and the reaction temperature is again maintained at 75°C for about 3 hours until no incyanate is detectable in the reaction 6&compound.

The prepolymer is then filled into metal cans, degassed, flushed with nitrogen, and stored for further compounding.

Example 2 Silane wood end prepolymer was synthesized as follows.

Product name [Polym@g 1000J Polyoxytetramethylene diol (molecular thlIk21000) 389.2g (0.77Jk)
), 4,4'-diphenylmethanediyn 7anate 76
．． 9! i (0.62 equivalent t), toluene 57.4 Iis”
and diptyltin dilaurate o, ozI as a catalyst.
! Mix thoroughly in the v reactor. The mixed ingredients were then heated at 75° C. for about 3 hours or until no isocyanate groups were detectable in the reaction mixture. After Mk, isocyanatoalkoxy 7 run 38
．． 0 g (0.15 eq.) was added.

The mixture was again held at 75° C. for 6 hours until no NGOs could be detected by infrared analysis.The prepolymer was then placed in a metal can, degassed and flushed with nitrogen for 7 hours.
Lashed and stored.

Example 3 A polyurethane packbone-containing polymer having r-incyanatoglobiltrimethoxysilane as the end group in place of the r-incyanatoglobiltriethoxysilane of the previous example was produced as follows. It has a hydroxyl equivalent weight t- of 1840 and has a trade name of "Olin (01in)".
) Polyether diol 283.011 (0,15 equivalents) commercially available as Poly-G-55-304
, 4.4-dipheelmethane diinocyane) 9.6
II (0.077 g) and 0.02 p of diptyltin dilaurate as catalyst were thoroughly mixed and heated at 75° C. for 3 hours until no isocyanate absorption was observed in the infrared spectrum.

15.8 p (0.07 eq.) of r-isocyanatoprobyl trinotoxysilane are then added and the whole mixture is again kept at 75° C. until there are no more incyanate groups present by -c detection by infrared analysis. Heated for 5 hours. The prepolymer was placed in a metal can, degassed, flushed with nitrogen, and stored for further compounding.

Example 4 A 5-terminated polyester prepolymer was produced as follows. Polycaplactone diol 745, which has a hydroxyfur equivalent weight of 267 and is commercially available under the trade name rpcp-0200J! l (2,78 equivalents)
, 4.4'-diphenylmethane diisocyanate 322
．． 4.9 (2,55 electric current) and toluene isa, o
II was thoroughly mixed in a scintillator. The mixed components were then heated at 75° C. for 3 hours until no incyanate groups were detectable in the reaction mixture. Finally r-
incyanatoalkoxysilane 57.511 (0,23
equivalent amount) was added. The mixture was again kept at 75° C. for 8 hours until no inocyanate absorption was observed in the infrared spectrum. The prepolymer was then placed in a metal can, degassed, flushed with nitrogen, and stored.

Example 5 A silane-terminated branched polyether prepolymer was produced as follows. In a reaction vessel, polyether diol 12024N (12 equivalents) and 4,4'-diphenylmethane diisocyanate) 1764II (14
(equivalent), and a mixed plasticizer 6036j consisting of 310# alkylnaphthalene monomer and 5726 g of cy C11-dialkyl 7-talate were combined. - Heat the combined ingredients to 63°C, stop heating and add triethylene cyanocatalyst 41i, then bring the temperature of the reaction mixture to 75°C, and at this temperature
It was held for 0 hours. NGO content/amount is 0.4, which is equal to the theoretical value
It was found that 254. At this point, polyether triol 5osB (sai amount) and further triethylenediamine/catalyst 14Ii were added to the reaction mixture.

A temperature of 55° C. was maintained for 3 hours, at which time no incyanate could be detected by infrared spectroscopy.

Finally, Incianato Alkoki 7sila 7988, @(4
i amount) and further triethylenediamine/catalyst 4j were added. The resulting mix*1 was brought to a temperature of 75-80<0>C and held at this temperature for an additional 3 hours or until no isocyanate content was detected.

The prepolymer was then filled into metal canisters, degassed, flushed with nitrogen, flushed, and stored.

Example 6 A silane-terminated branched polyether prebolimer was synthesized as follows. In the reactor 182.2 g (0.18 eq.) of polyether diol, 26.7 Ii (0.21 i amount) of 4.4/-diphenylmethane diisocyanate
and c, C11-dialkyl phthalate) 91.5
．． p, and triethylenediamine as catalyst 0.2
4.9 and a small amount of defoamer were combined. The reaction mixture was heated at 75°C for about 8 hours. The NGO content was found to be 0.42%, which is equal to the theoretical value. Then a polyether triol 149.1 (0.0 g equivalent) produced from glycerin and propylene oxide and having a hydroxyl equivalent weight of 1644 and commercially available under the trade name "Pullacol 816" and a triethylenediamine catalyst 0 .12/i was added to the reaction mixture.

The temperature of 55°C was maintained for 3 hours or until the incyanate groups were no longer detectable by infrared analysis. Finally, r
-Ino7anatoalkoxysilyl 5. Og(0,0
6 equivalents) was added. Heat the entire mixture 1 to 75°C,
It was then held at this temperature for an additional 6 hours until no incyanate content was detected. The prepolymer was then placed in a metal can, degassed, flushed with nitrogen for 7 hours, and stored.

Example 7 The following polymer has a linear polyether backbone and contains aliphatic urethane linkages along with urea groups.

Inphoron diisocyanate) 416.6g (3,75
equivalent) to 95°C, then surfactant 0,'15
1. It was combined with 0.08 Ji' of diptyltin dilaurate catalyst and 0.02 Ii of triethylenediamine as catalyst. After thorough mixing, 8.5ti (0.94 equivalents) of water was slowly added to the mixture at a rate of approximately 111thii every 10 seconds. The temperature of the mixture was maintained at 95°C during the addition of water.

Once the water addition was complete, heating was stopped and the reaction mixture was slowly cooled to room temperature with stirring.

The product was 29.111% compared to the theoretical value of 27.8%.
(the high value of NCO is due to the loss of water during the reaction).

Based on the incyanate content determined in this way, the number of equivalents of the reaction mixture was calculated and polyether diol 3606.59 (3,51 equivalents) was added to N
9 giving a slight excess of hydroxyl groups with respect to GO. At the same time, 0.38 f/t of dibutyltin dilaurate catalyst was added to the mixture, then heated to 75 DEG C. and maintained at this temperature for 8 hours until no more isocyanate could be detected in the reaction hot metal.

Finally, isocyanatoalkoxysilane 172.1 (
0.70 equivalent ft) was added. The mixture was again kept under odor at 75° C. for 8 hours until NGO could no longer be detected.

One prepolymer was then filled into metal cans, degassed, rinsed with nitrogen, and stored for further compounding.

Example 8 An alkoxysilane terminated polymer similar to that of Example 7 and consisting of a linear polyether structure having both urea groups and aliphatic equanate groups was produced as follows. 1194.7 g (9.13 molar mass) of dicyclohexyl-4#4'-methaneshiinoaanate was added to 95 m
heated to ℃. Surfactant “Igepal (Ig@pa1)
month 2.01i, diptyltin diphucrate catalyst 0.2.
9 and triethylenediamine catalyst 0.5 gk/fi
I did MJ. Next, 10.4 g (1,13 g) of water was added to 1
7 Jl] was gradually added at a rate of about 1 drop every 0 seconds. The temperature of the pot was maintained at 95°C during the addition of water.

Once the addition was complete, heating was stopped and the reaction mixture was slowly cooled to room temperature with stirring. The reaction product obtained had an isocyanate content of 28.7%, from which the percussion weight 1 of the reaction mixture was calculated to be 146.4.

Polyether diol 10108.1 g (10 equivalent tons)
Diptyltin t-diturate was added to the mixture along with 0.16 g. The mixture was heated to 75 DEG C. and maintained at this temperature for 16 hours - or until no more incyanate was appreciably detectable. Since a slight excess of diol is used, the resulting product is hydroxyl terminated.

And incyanato alkoxysilane 494.0p (
2 equivalents) and 0.169 g of antifoam were added and the mixture was again held at 75° C. for 64 min or until no isocyanate was detectable.

The resulting prepolymer was filled into metal plates, canisters, degassed, flushed with nitrogen, sealed, and stored in balls for further compounding.

Example 9 A polymer having a polyether structure consisting of urea groups and aliphatic urethane groups and 94 ethoxysilane wood end groups per molecule was synthesized as follows.

Isophorone digosoquanate and water in the presence of surfactants, diptyltin dilaurate and triethylenediamine? A urea group-containing adduct was produced by reacting as described in I7. Then 27.0 g (0.93 eq.) of this adduct, 162.3 N (0.80 eq.) polyether diol, and Dibutyltin diurate catalyst 0.041s antifoam agent 0.0211
s Alkylnaphthalene plasticizer 4.1g, Oyohi c t
y-C1l-dialkyl 7-thalerate plasticizer 812I and 5
00- in a reaction vessel and heated to 75°C;
And hold at the temperature for 3 & 9 hours. The incyanate content of the reaction mixture was determined to be 0.51-.

and polyether triol 118.4.9 (10
, 4 equivalents) was added to the dibutyltin dilacrylate catalyst.
and the reaction mixture was heated again at 75° C. for 3 hours until no incyanate was detectable in the mixture.

Finally, disilane 13.211 in incyanatoalco (
0.27@quantity) and product name [Formr
@m) Adding 0.04 g of dialkyltin dicarboxylate catalyst commercially available at UL 28 J;
The mixture was then heated again at 75° C. for 3 hours until incyanate could no longer be detected.

The reaction mixture is then filled into metal cans under nitrogen and sealed for storage.

The following discussion relates to the use of the prepolymers produced in the above examples in the formulation of sea tent compositions.

Example 10 A sealant composition was prepared using IPil as follows.
62.2 parts of the prepolymer of Example 1 and 0.634 parts of dibutyltin acetate were combined in a planetary mixer and placed under nitrogen to exclude moisture.
Mixed for 0 minutes.

In this respect, 2.83 parts of N-(β-aminoethyl)-r-aonoglobil trimethoxysilane, 0.63 g of tris-(dimethylaminomethyl)phenol as optional catalyst and 2.93 parts of xylene , and 1.57 parts of methanol, and mixed the new mixture for 20 minutes. All ingredients added in this step were carefully dried in a ball to avoid introducing moisture into the composition.

Finally, 14.72 parts dry carbon black and 14.72 parts dry clay were added to the mixture and 19 inches Hg
Mixing was continued for an additional 20 minutes under reduced pressure (approximately 483-Hg). The sealant formulated in this manner was filled into a sealant tube.

The resulting sealant contains only 4.5% by weight of solvent so that the shrinkage due to solvent evaporation after curing is no greater than 4.5%. Sealants do not cause any lumps. The cure rate (rats) of the sealant was 36.0 ps in 2.7 hours, as measured by the following rapid adhesion test:
It was l.

For rapid adhesion testing, extrude onto a plate of sealant. Spray this assembly with water and place it on top of another primed glass plate t7-runt beet for 1 hour at room temperature.
Allow to cure for an hour and then immerse in a water bath for 4 minutes at 771°C (approximately 25°C). The plates are then separated by pulling in the plane of #1 against the plane of the bead 2.7 hours after the assembly time. Cure rate is recorded in psl over elapsed time.

11 A sealant comprising the prepolymer of Example 1 was formulated with a quaternary ammonium hydroxide accelerator to form a sealant composition suitable for rapid room temperature curing.

Prepolio-61,62 of Example 1 as in Example 10
and diptyltin diacetate, o, atg, are combined in a planetary mixer and set to form N-(β ~ annoethyl).
-r-aminopropyltrimethoxysilane 2.80p,
0.62 parts of tris-(dimethylaminomethyl)phenol and 2.2 parts of xylene as optionally added catalysts.
90 fl, and 2.58 parts of benzyltrimethylammonium hydroxide (40% in methanol) were mixed before addition.

After mixing for an additional 20 minutes, dry carbon black 14.
57 g and 14.57 parts of dry clay were added to the mixture, and the formulation was again heated to 19 inches Hg (approximately 483 mH).
g) Mixed for 20 minutes under O vacuum.

Sealants formulated in this manner did not drip. The curing speed in the rapid contact test was 2.7 after assembly.
Curing rate, measured in hours, for a material of the same content without a quaternary ammonic hydroxide promoter: 36
．． It was 77.0 psi compared to 0 psi 4C.

The lap shear strength of the composition was tested by bonding two primed glass plates.

Each measures 1 inch x 5 inches x O, 25 inches (approx.
54 on X 12.7 cat X O, 643)
The sealant was applied from a tube along one of the edges of the glass plate, having a length of approximately 1 inch (approximately 1 inch).

The glass plate compressed the sealant into a sandwich. The samples are allowed to cure for several days at room temperature and then separated by pulling in a plane parallel to the plane of the bead. In this trial, the fake sealant was 300~
2 of 400psi. It shows the shear strength f.

Example 12 Using the formulation described in Example 10 above, yet another sealant was prepared from the prepolymer of Example 7 as follows.

That is, 61.28 parts of the prepolymer of Example 7 are first combined with 0.33 g of diptyltin diacetate catalyst and mixed thoroughly. Thereafter, 3.34 g of N-(β-aminoethyl)-r-antnoprobyltrimethoxyfufur, )lis-(
0.61 parts of dimethylaminomethyl)phenol, 2.90 parts of xylene and 2.56 parts of benzyltrimethylammonium hydroxide (40% in methanol) are added and mixing is continued for a further 20 minutes.

Finally, 14.49 parts of dry carbon black and 14.49 parts of dry clay are added and the resulting mixture is mixed again under partial vacuum for 20 minutes.

The resulting sealant did not produce any lumps.

Cure measured by rapid adhesion test for sealant averaged 74.0 psl 2.7 hours after assembly
Met. Two sheets of beads laid down on glass showed interlayering for several days at room temperature.

Example 13 N-(β-aminoethyl) -N/-(?
'-)rimethquine7lylglovir)-ethylenediamine and using the formulation described in Example 10 above,
Sealant was prepared from the prepolymer of Example 1. fll
66.40 parts of prepolymer were thoroughly mixed with 0.34 fm of diptyltin diacetate catalyst. , N − (β
-aminoethyl)-N'-(r-trimethoxy7lylglovir)-ethylenediamine 1.13 parts, benzyltrimethylammonium hydroxide (40 parts in methanol)
%), 1.36 parts of dry methanol, and 2.76 parts of dry toluene were added and mixing was continued for an additional 20 minutes. After j&, 13.25511 dry carbon black and 13.25 parts of dry clay were added and the whole mixture was mixed again under ^9 for 20 minutes.

The cure rate of the sealant thus prepared (as measured by rapid adhesion test) averaged 127 psi at 3.5 hours after assembly.

Patent applicant: Ese, Kusu Chemical Corporation, N

Claims (25)

[Claims] (1) Moisture-curing property characterized by reacting a polyurethane prepolymer having terminally active hydrogen atoms with an incyanato organic compound having terminal isocyanate groups and at least one hydrolyzable alkoxy group bonded to silicon. Method for producing silicon powder polymer. (2) The method of claim 1, wherein the incyanato organosilane has 1 to 3 hydrolyzable alkoxy groups bonded to silicon. (3) The incyanato organosilane has the formula 0% (1
) (In the formula, s Ri is a divalent organic group, n'la is hydrogen or an alkyl having 1 to 4 carbon atoms, and X is a carbon number 1
2. The method of claim 1, wherein the hydrolyzable alkoxy 1 is a compound of 1 to 4, and m is an integer from 1 to 3. (4) The isocyanato organic 7-rane bonded to silicon and having at least one hydrolyzable alkoxy group is r
-iso7anatoprobyltriethoxy7rane. The method according to claim 1. (5) The polyurethane prepolymer has terminal ends.
8Hfitake-NH, the method according to claim 1, having a group. 6. The method of claim 1, wherein the polyurethane prepolymer has terminal --OH groups and is produced by reacting excess polyol with an organic polyisocyanate. (7) The method according to claim 6, wherein the polyol is a polyether polyol. (8) The method according to claim 7, wherein the polyether polyol is a polyether diol. (9) The method according to claim 8, wherein the polyether diol is a polyoxyalkylene diol. (10) The method according to claim 7, wherein the polyether polyol is a mixture of polyether diol and polyether triol. (11) The method according to claim 1θ, wherein the polyether diol is a polyoxyalkylene/diol69, and the polyether triol is a polyoxyalkylene triol. (12) The polyurethane prepolymer is terminally terminal with -〇■ groups and also has urea groups in the polymer chain, and is produced by reacting an excess mixture of polyol and water with an organic polyic anate. The method according to claim 1. (13) 25 of the total hydroxyl equivalents in the mixture
13. The method of claim 12, wherein up to 1. (14) The method according to claim 6, wherein the polyol is a polyester polyol. (15) The method according to claim 14, wherein the polyester polyol is a polyester diol. (16) The method according to claim 15, wherein the pre-E polyester diol is a polyalkanol diol. (17) A non-moisture curable silicon-terminated organic polymer produced by the method according to claim 1. (18) Moisture-curable silicon terminal 1 produced by the method described in claim 4! machine polymer. (19) A moisture-curable sealant composition comprising the moisture-curable silicon-terminated organic polymer according to claim 17 and at least one filler. (20) The sheeting composition according to claim 19, characterized by a curing catalyst for the silicon-terminated organic polymer. (21) The sheeting composition according to claim 20, wherein the catalyst is a quaternary ammonium hydroxide. (22) The sealant composition according to claim 21, wherein the catalyst is benzyltrimethylammonium hydroxide. (23) The sealant composition according to claim 19, characterized by an aminoorganosilane having at least one hydrolyzable alkoxy group bonded to silicon. (24) The sealant composition according to claim 23, when the amino silane is N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane. (25) The sealant composition according to claim 23, wherein the amino acid is N-(β-aminoethyl)=N'-(r-trimethoxysilylglobyl)-ethylenediamine.